Solvent treating process



April 21, 1942.` E. D. REEvEs ,2,280,264 soLvENT TEEATING PRocEss l Fil'ed Aug. 19,- 1939 vILIEM TER Il l Muir 25 2'6 27 www a n .uyV .1355.

Patented Apr. 2l, 1942 SOLVEN T TREATING PROCESS `Edward D. Reeves, Cranford, N. J., assignor to Standard Oil Development Company, a corporation of Delaware Application August 19, 1939, Serial No. 290,956

7 Claims.

The present `invention relates to the solvent treatment of mineral oils. It is especially concerned with an improved process of solvent treating petroleum oils in which the selective solvent` is recovered from the respective phases without the necessity of distillation. In accordance with the present invention petroleum oils are treated with primary solvents selectedfrom the class of solvents which have a preferential selectivity for the relatively more aromatic or hydrogen poor constituents as compared to the relatively more paraiiinic or hydrogen rich constituents under conditions to form raffinate and solvent` extract phases. The respective phases are separated and treated with an aqueous inert salt-solution under conditions to remove the selective solvent from the oil.

It is well known in. the art to treat petroleum oils and the like with various selective solvents which have the ability to segregate these oils into their respective constituents as measured by a difference in chemical and physical properties.

For example, it is known to treat petroleum oils with solvents or solvent mixturesselected from the` class of solvents which have a preferential phenol, furfural, sulfur dioxide, cresol, nitrobenzene, aniline, beta beta dichlor diethyl ether, Aand the like. It is also known to use these solvents incombination with other substances, as for example, in combination with `liquid normally gaseous hydrocarbons such as propane and the like. It is also known to modify the selectivity and solvent power of the particular solvent or solvent mixture being used by the addition thereto of a solvent'modifying agent such as-watei", alcohols, glycols, and the like. Although a batchor semibatch operation is entirely satisfactory for contasting the o-il and solvent. the usual commercial practice is to contact the oiland solvent in a countercurrent tower treating process. In this operation, the heavier phase, usually the solvent, is introduced into the top of a lcouhtercurrent treating tower, while the lighter phase, usually the oil, is introduced into the bottom or center portion of the countercurrent treating tower.

These phases flow in a countercurrent relation-l fil) by the addition of various precipitants.

ship. Eflicient contacting between the countercurrently flowing phases is usually secured by suitable contacting and distributing means, as for example, pierced plates, contacting masses, distributing trays and the like. Temperature and pressure conditions are adjusted to form a solvent poor or rafnate phase relatively highly paraflinic in nature and a solvent rich or extract phase highly aromatic in nature. The respective phases are separated and the solvent usually separated from the extract and raffinate respectively by distillation.

The removal of the solvent from the rafnate and `extract phases by distillation introduces economic limitations since solvents which have desirable selectivity `characteristics have relatively high latent heats of vaporization. Thus, solvent treating operations `have been limited to some extent by the costs of the recovery of the selective solvent from the treated oil. In order to lower operating costs and to create a more widespread application of solvent treating operations, numerous proposals have been made in order to eliminate or modify the distillation step. For example, it has been proposed to re-extract the solvent extract and ranmate phases with various secondary solvents of relatively low latent heats and which have a preferential selectivityv for the raffinate and extract respectively as compared to the primary solvent. This process likewise has not been entirely satisfactory since known secondary solvents do not completely remove the last traces of the highly aromatic constituents from the primary solvent. Thus, the concentration of the highly aromatic constituents continuously builds up in the primary solvent, necessitating replacement or purification of the same by distillation or `the like. In addition, the quantity of secondary solvent required is quite large, thus ofi-setting to some extent the resulting economies secured by the removal of the primary solvent by ire-extraction, rather than by distillation. It is also known to separate the primary selective solvent from the raiilnate and solvent extract phases These operations have not been used to any extent since an excessive amount of precipitant is required in order to secure fairly complete precipitation of the oil. Washing operations likewise have been employed for the recovery of the selective solvent from the respective phases. For example, it is known to remove phenol from a phenol petroleum oil mixture by treating said mixture with a relatively large amount of water which will dissolve the solvent and separate the same from the oil. These processes also are not entirely satisfactory since a relatively large amount oi Water is required and the subsequent separation of the Water from the phenol presents serious problems.

I have now discovered a process of recovering the primary solvent in a highly purified state in an economical manner Without the necessity of distilling the same. My process comprises a twostage operation in which a heated aqueous inert salt solution is added to the respective phases. The hot aqueous inert salt solution is completely miscible with the selective solvent and causes substantially complete precipitation of the oil from the resulting solvent -aqueous salt solution' phase. The raffinate and extract are separated from the solvent aqueous salt solution phase, which latter phase is then cooled, thus causing the formation of an aqueous inert salt layer and a primary selective solvent layer. The selective solvent is separated from the aqueous inert salt layer and recycled to the system, either with or without further drying.

The process of my invention may be readily understood by reference to the attached drawing illustrating one modication of the same. Feed oil, which for the purposes of description is assumed to be a petroleum lubricating oil, is introduced into primary extract tower I by means of feed line 2. The feed oil flows upwardly through tower I and contacts downlowing solvent which is introduced into tower I by means of feed line 3. The solvent, for the purposes of description, is taken to be phenol. Temperature and pressure conditions in tower I are adapted to secure theformation of a solvent poor or raffinate phase and a solvent rich or solvent extract phase. Water which may contain some phenol, may -be introduced into tower I at a plurality of stages,

, preferably above and below the oil feed inlet, by

means of lines 4, 5, 6, 1, and 8 respectively. The raffinate phase is Withdrawn from tower I by means of line 9 and pump I0. The rafnate phase is then mixed with a sucient quantity of aqueous inert salt solution which is introduced by means of line II. For the purposes of description the aqueous inert salt solution is taken to be an aqueous solution of sodium chloride. The mixture passes through heater or cooler I2, through mixer I3, and then into separator I4. The oil phase containing a relatively small amount of phenol is withdrawn from separator I4 by means of line I5, heated by means of heater I6 and then introduced into raffinate stripper I1. Steam is introduced into rafnate stripper Il by means of line I8 in order to remove the last traces of phenol. The solvent-free rainate is withdrawn from raffinate stripper II by means of line I9. The solvent and steam are removed from raflinate stripper I'I by means of line 20, condensed in condenser 2! and then mixed with the phenol-water-sa-lt phase which is withdrawn from separator tank or centrifuge I4 -by means of line 22. The solvent extract phase is withdrawn from tower I by means of line 23 and treated in a similar manner. The solvent extract is mixed with a sufficient quantity of an aqueous solution of sodium chloride introduced into line 23 by means of line 24. This mixture is then heated or cooled in 25, passed through mixer 26 and then introduced into extract separator 21,

The oil phase containing a relatively small amount of the solvent is Withdrawn from extract separator 21 by means of line 28, heated in heater 29, and then introduced into extract stripper 30. It may be desirable to return a portion of the oil phase to tower I by means of line 3|. Steam is introduced into extract stripper 30 by means of line 32 in order to remove the last traces of solvent from the extract. Solvent-free extract is withdrawn from extract stripper 3Q by means of line 33 and the stripped solvent and steam removed overhead by means of line 34. The phenol-water-salt phase is removed from extract settling tank or centrifuge 2l by means of line 35 and mixed with the solvent-watersalt phase Withdrawn from ranate settling tank or centrifuge I4 along with the overhead removed from extract stripper 30 by means of line 34. The combined solvent-water-salt phases from separator tanks I4 and 21 along with the overheads from railinate stripper Il and extract stripper 30 are then chilled in Chiller 36 and introduced into solvent, aqueous salt solution separator 31 by means of line 38. The aqueous salt solution is removed from separator 3l by means of line 39 and introduced into aqueous salt solution storage 40. The phenol layer from separator 31 is introduced into phenol drier 4I by means of line 42. Phenolic water is removed overhead from drier 4I and is preferably introduced into the countercurrent treating tower I by means of line 43. If an excess of water be removed overhead from solvent drier 4I, the excess may be introduced into aqueous salt solution storage 40 by means of line 44. Phenol containing a small `amount of water and a concentrated solution of salt in water is withdrawn from drier 4I and introduced into separator 45 by means of line 46. The water phase containing the concentrated salt is removed from separator 45 by means of line 41 land introduced into aqueous salt storage 40. The phenol substantially free of water, oil and salt is recycled to line 3 by means of line 48. Fresh phenol may be introduced into the system by means of line 49.

The conditions and method of operating in accordance with the present invention may be Widely varied. The invention is applicable in the solvent treatment of petroleum oils, although particularly desirable results are secured in the treatment of petroleum oils boiling in the lubricating and gas oil ranges. The invention is particularly applicable in the removal of selective solvents of the character of furfural or in the removal of phenolic type solvents, as for example, phenol, cresols, and the like. The aqueous salt solution with respect to the particular salt being used, the concentration of the salt in the solution, and the quantity of the solution used per volume of oil being removed likewise may vary considerably. Satisfactory salts are those salts which are inert and will not react with the particular selective solvent, as for example, sodium chloride, potassium chloride, or sodium sulphate.

'Ihe quantity of primary solvent used will vary considerably, depending upon the particular solvent used, as well as upon the petroleum oil being treated and the yield andquality of products desired. In general, it is preferred to use from one-half to four volumes of solvent per volume of oil being treated, although as much as ten volumes .or more of solvent can also be used since excessive distillation costs are avoided by my process.

`It ispreferredfto introducel 'the solventv either dry or containing a low concentration of Water at one end of the countercurrent treating system which| may beeither a column or a series of stages. Wateris .injected preferably'iat a plurality of points above or below or on each side of the stage at which the feed oil is introduced. The quantity of water introduced will depend upon the oil being treated, the solvent` being used, as well as upon the temperature and pressure conditions employed. Whentreating' alubricatin'g oil distillate with phenol, it is preferred to introduce from 3% to 15% of water, based upon the solvent being used. Temperature and pressure conditions in the countercurrent treating systemwill likewise vary, depending upon the/solvent being used, `the character of the oil being treated, and the yield and quality .of products desired. In general, atmospheric pressure or a pressure sufficient to maintain all materials in the liquid phase and a temperature below `the complete miscibility temperature and above the melting pointof the solvent are employed. For example, when employing phenol asthe selective solvent, it is preferred to maintain a temperature throughout the tower in the range from about 80 F. to 250 F.

The amount cf. aqueous salt solution added to the .raiiinate phase will depend upon the above named factors and upon the concentration of the salt` present. In general, it is preferred to add from V% to 20% of sodium chloride solution, based upon the totalquantity of raffinate. The rainateiphase and the salt water are then heated to a temperature at which an oil phase will separate substantially free of solvent. It has been found, for example, that when 10% to 20% of 1.5 to 2.0% concentrated sodium chloride solution vis added, based upon the total volume of raflinate, and when using phenol as the selectivesolvent, especially desirable results Aare Vsecured when the mixture is heated toa temperature in the neighborhood of about 200 F. The concentration of sodium chloride in the aqueous salt solution should be in the range from about 1/2% to 4% and should preferably not exceed about 2%. The temperaturesmaintained in the raffinate stripper and the quantity of steamin-` troduced into said stripper are adjusted to iproduce a solvent-free rainate.

The quantity of salt solution added to the However,` in -order` to secure a desirable ecoi tive solvent and when adding from to 150%l byvolume of sodium chloride solution, based uponthe total volume of extract phase, it has been found that desirable results are secured by heating the aqueous salt extract mixture to 'a temperature in the range from about 175 F. `to 225 F. The temperature of the extract stripper and the quantity of steam introduced into said stripper are adjusted to `produce -a solvent-free extract.

The invention, "however, is particularly directed Y and applicable in -th-e Aremoval of phenol `from the` respectivephases; by :means of ari-aqueous sodium'chlioridef-solutiong-in which case the concentration foff the sodium chloridein the :solution and the operating temperature are critical. I have found that in order. to secure satisfactory results, the concentration of the sodium chloride should be inthe range of about lll/2% to 2%. I have also found that at a temperature in the range Ifrom about 175 F.to 225 F., preferably at a temperature of about 200'.F., phenol is completely miscible andsoluble to the exclusion of oil inan aqueous sodium chloride solution of the above-mentioned concentratiom and at a temperature in the range from about F. to 125 F. is substantially fully precipitated from said sodium chloride solution.

.In vorder to further illustrate the invention the following examples are given which should not be construed as limiting the same in any manner whatsoever: f

Example 1 .Several operations were conducted in recovering spent phenol containing 12% extract in which various amounts of-water containing different percentages of sodium chloride `were used in removing the selective solvent-from the oil. These operations were conducted at 200 F. with the results as follows:

From the above data it is to be observed that the amount of oil in the recovered phenol was reduced 40% when usingl 200 volume per cent of a 2% sodium chloride solution.

`It was noticed that a clear separation of oil from the phenol Wasunot Vobtained with pure water, even when large amounts were used, while the addition of a small amount of sodium chloride resulted in a clear separation.

Example 2 The effect of the salt concentration on the settling time was determined using a 400% `wash at 200 F. on a spent phenol containing 12% oil.

TABLE 2 Volume percent oil separated Percent N aCl in wash l min. 5 min. l5 min. 30 min.

It will be noted that only about 50% of the oil is removed in 15 minutes settling time when pure water is used, while nearly complete re- `moval is obtained when 1.0% salt is added tothe water.

Example 3i A petroleum oil having a gravity of about 25 A. P. I., a Saybolt viscosity of 450 seconds at 100 F., and about 60 seconds at 200 F. when treated with 2*.parts by Volume of phenol at a temperature of about 140 F. in accordance with the process of the present invention results in the following material balance:

TABLE 3 Primary extraction tower Total volumes feed Total withdrawn Water Rainate Extract ou Phenol injected phase phase '10ta1 A-313 31a Ranate separator Feed Phases withdrawn Raninate 27 sodium vphase chloride Total Rainate .Pvll from water feed phase phase tower injected Ranate stripper Feed Withdrawn Rglte Steam Raffinate Overhead Oil 75 75 Phenol. 2 2 Water 2 2 Total 79 79 Extract separator Feed to phenol-sodium chloride solution separator Eesti? Pvvltllel' Overhead Overhead phase from phase from rafiiiirte eifrrt'lat 'Ifebl extract raffinate t stri er separator separator s upper pp Oil 2 2 PhenoL- 191. 5 24. 5 2 2 220 Water l5 2 2 204 Withdrawn from phenol sodium chloride separarater Aqueous Phenol water sodium hase to chloride to I? o1 d Storage p en ner Total 426 Phenol drier Withdrawn Il Bottolrns l Recycled Onp gno Feed phenolic ner o concentrated Water solution separator The process of the lpresent invention is not to be limited in any manner whatsoever, but only by the following claims in which it is intended to claim all novelty in so far as the prior art permits.

I claim:

1. Process for the removal of the selective solvent from the ranate and extract phases respectively secured in the solvent treatment of mineral oils When utilizing a water soluble selecrtive solvent comprising treating the respective phases with a hot aqueous inert inorganic salt solution under conditions to separate an oil phase and a selective solvent aqueous salt solution phase, separating and cooling said latter phase whereby a selective solvent phase and an aqueous salt solution phase form, separating said latter phases and recycling the same to said solvent treating process.

2. Process in accordance with claim 1 in which said selective solvent is a phenol.

3. Process in accordance with claim 1 in which said selective solvent is a phenol and said inert salt is sodium chloride.

4. Process for the removal of phenol from the rafnate and extract phases respectively secured in the solvent treatment of mineral oils comprising treating the respective phases with a hot sodium chloride solution, said concentration of sodium chloride being in the range from 11/2% to 4% under conditions to separate an oil phase and a phenol sodium chloride solution phase, separating and cooling said latter phase whereby a phenol phase and an aqueous sodium chloride solution phase form, separating said latter phases the range from 11/2% to 2%, whereby an oil phase and a phenol sodium chloride solution phase form, separating the phenol sodium chloride phase and cooling to a temperature of about 100 F. whereby a phenol phase and a sodium chloride solution phase form, separating said latter phases and recycling the same.

7. A process according to claim 6 wherein about 10% to 20% of the aqueous sodium chloride solution is added to the ranate phase and about 50% to 200% of the aqueous sodium chloride solution is added to the extract phase.

EDWARD D. REEVES. 

